Acylated 5-aminopyrazoles and the use thereof to combat animal parasites

ABSTRACT

The present invention relates to new acylated 5-aminopyrazoles of the formula (I) ##STR1## in which R 1 , R 2 , R 3 , R 4  and R 5  have the meaning given in the description, 
     to processes for their preparation and to their use as pesticides.

This application is a divisional of Application Ser. No. 09/145,532,filed Sep. 2, 1998 (now U.S. Pat. No. 5,981,566), which is a division ofSer. No. 08/875,060, filed Jul. 7, 1997 (now U.S. Pat. No. 5,843,978),which is a 371 of PCT/EP95/05148, filed Dec. 28, 1995.

The present invention relates to new acylated 5-aminopyrazoles, toprocesses for their preparation, and to their use for controlling animalpests, in particular insects, arachnids and nematodes found inagriculture, in forests, in the protection of stored products and ofmaterials, and in the hygiene sector.

It has already been disclosed that certain 1-aryl-5-aminopyrazolederivatives (cf., for example, EP-A 0 257 479 and EP-A 0 243 636) haveinsecticidal and acaricidal properties.

However, efficacy and spectrum of action of these compounds is notalways entirely satisfactory, in particular when low rates andconcentrations are applied.

There has now been found new acylated 5-aminopyrazoles of the formula(I) ##STR2## in which R¹ represents alkyl, alkoxyalkyl or halogenoalkyl,

R² represents hydrogen, halogen, cyano, nitro, halogenoalkylthio,alkoxycarbonyl or alkenyloxycarbonyl,

R³ represents alkyl or optionally substituted cycloalkyl,

R⁴ represents hydrogen, alkyl or optionally substituted cycloalkyl and

R⁵ represents the group --Y--R⁶, where

Y represents optionally substituted alkanediyl and

R⁶ represents in each case optionally substituted aryl or aryloxy.

Furthermore, it has been found that the acylated 5-aminopyrazoles of theformula (I) are obtained when

a) 5-aminopyrazoles of the formula (II) ##STR3## in which R¹, R², R³ andR⁴ have the abovementioned meaning

are reacted with acid halides of the formula (III)

    R.sup.5 --CO--Hal                                          (III)

in which

R⁵ has the abovementioned meaning and

Hal represents halogen

in the presence of a base and in the presence of a diluent;

or

b) acylated 5-aminopyrazoles of the formula (Ia) ##STR4## in which R¹,R³, R⁴ and R⁵ have the abovementioned meaning

are reacted

(α) with a halogenating agent, if appropriate in the presence of adiluent and if appropriate in the presence of a catalyst,

or

(β) with a nitrating agent, if appropriate in the presence of a diluent.

Finally, it has been found that the new acylated 5-aminopyrazoles of theformula (I) have pronounced biological properties and are suitable,above all, for controlling animal pests, in particular insects,arachnids and nematodes, which are found in agriculture, in forests, inthe protection of stored products and of materials, and in the hygienesector.

Formula (I) provides a general definition of the acylated5-aminiopyrazoles according to the invention.

Preferred substituents or ranges of the radicals given in the formulaementioned hereinabove and hereinbelow are illustrated in the followingtext.

R¹ preferably represents C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₄ -alkylor C₁ -C₄ -halogenoalkyl.

R² preferably represents hydrogen, halogen, cyano, nitro,trifluoromethylthio, difluoromethylthio, C₁ -C₄ -alkoxycarbonyl or C₂-C₄ -alkenyloxycarbonyl.

R³ preferably represents C₁ -C₄ -alkyl, or represents C₃ -C₆ -cycloalkylwhich is optionally substituted by halogen or C₁ -C₄ -alkyl.

R⁴ preferably represents hydrogen, C₁ -C₄ -alkyl, or represents C₃ -C₆-cycloalkyl which is optionally substituted by halogen or C₁ -C₄ -alkyl.

R⁵ preferably represents the group --Y--R⁶ where

Y represents C₁ -C₄ -alkanediyl which is optionally substituted byhalogen or C₃ -C₆ -cycloalkyl.

R⁶ preferably represents phenyl or phenoxy, each of which is optionallymonosubstituted to trisubstituted by identical or differentsubstituents, suitable substituents being halogen, nitro, cyano, C₁ -C₁₂-alkyl, C₁ -C₁₂ -alkoxy, C₁ -C₁₂ -alkylthio, C₁ -C₁₂ -halogenoalkyl, C₁-C₁₂ -halogenoalkoxy, C₁ -C₁₂ -halogenoalkylthio, C₂ -C₁₂ -alkenyl, C₁-C₁₂ -alkoxy-C₂ -C₁₂ -alkenyl, C₁ -C₄ -alkylthio-C₂ -C₁₂ -alkenyl, C₂-C₁₂ -halogenoalkenyl, and also phenyl, phenoxy, phenylthio or benzyl,each of which is optionally monosubstituted to trisubstituted byidentical or different substituents from the series consisting ofhalogen, nitro, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio,C₁ -C₄ -halogenoalkyl, C₁ -C₄ -halogenoalkoxy or C₁ -C₄-halogenoalkylthio.

R¹ especially preferably represents methyl, ethyl, n- or i-propyl or n-,i-, s- or t-butyl; or represents methoxymethyl, ethoxymethyl,methoxyethyl, ethoxyethyl, trifluoromethyl, difloromethyl, fluoromethyl,1-chloro-1-ethyl or 1-fluoro-1-ethyl.

R² especially preferably represents hydrogen, fluorine, chlorine,bromine, cyano, nitro, trifluoromethylthio, difluoromethylthio,methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, n-, i-, s- ort-butoxycarbonyl or allyloxycarbonyl.

R³ especially preferably represents methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, or represents cyclopropyl, cyclopentyl or cyclohexyl,each of which is optionally substituted by fluorine, chlorine, methyland/or ethyl.

R⁴ especially preferably represents hydrogen, methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl, or represents cyclopropyl, cyclopentylor cyclohexyl, each of which is optionally substituted by fluorine,chlorine, methyl and/or ethyl.

R⁵ especially preferably represents the group --Y--R⁶, where

Y represents one of the groups --CH₂ --, --CH(CH₃)--, --CH₂ CH₂ --,--CH(C₂ H₅)--, --CH(C₃ H₇ --i)--, --CHF--, CHCl-- or--CH(cyclopropyl)--.

R⁶ especially preferably represents phenyl or phenoxy, each of which isoptionally monosubstituted to trisubstituted by identical or differentsubstituents, suitable substituents being chlorine, bromine, nitro,cyano, methyl, ethyl, n- and i-propyl, n-, i-, s- and t-butyl, methoxy,ethoxy, n- and i-propoxy, n-, i-, s- and t-butoxy, methylthio,trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy,trifluoromethylthio, difluoromethylthio, and also phenyl or phenoxy,each of which is optionally monosubstituted to trisubstituted byidentical or different substituents from the series consisting ofchlorine, bromine, nitro, cyano, methyl, ethyl, methoxy, ethoxy, n- ori-propoxy or n-, i-, s- or t-butoxy, trifluoromethyl, trifluoromethoxy,difluoromethoxy or trifluoromethylthio.

R¹ very especially preferably represents methyl, ethyl, i-propyl,t-butyl, methoxymethyl, 1-chloro-1-ethyl or 1-fluoro-1-ethyl.

R² very especially preferably represents hydrogen, chlorine, bromine,cyano, nitro, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl orallyloxycarbonyl.

R³ very especially preferably represents methyl, ethyl, i-propyl,t-butyl, or cyclopropyl.

R⁴ very especially preferably represents hydrogen, methyl, ethyl,i-propyl or cyclopropyl.

R⁵ very especially preferably represents the group --Y--R⁶, where

Y represents one of the groups --CH₂ --, --CH(CH₃)-- or --CH₂ CH₂ --.

R⁶ very especially preferably represents phenyl or phenoxy, each ofwhich is optionally monosubstituted or disubstituted by identical ordifferent substituents, suitable substituents being chlorine, bromine,nitro, cyano, methyl, ethyl, n- and i-propyl, n-, i-, s- and t-butyl,methoxy, ethoxy, n- and i-propoxy, n-, i-, s- and t-butoxy,trifluoromethyl, trifluoromethoxy and difluoromethoxy, and also phenylor phenoxy, each of which is optionally monosubstituted totrisubstituted by identical or different substituents from the seriesconsisting of chlorine, bromine, nitro, cyano, methyl, methoxy, ethoxy,n- or i-propoxy or n-, i-, s- and t-butoxy, trifluoromethyl,trifluoromethoxy, difluoromethoxy or trifluoromethylthio.

The definition of radicals and illustrations given above in generalterms or in preferred ranges apply to the end products and,correspondingly, to the starting materials and, intermediates. Thesedefinitions of radicals can be combined with each other as desired, thatis to say combinations between the respective preferred ranges are alsopossible.

Preferred compounds of the formula (I) according to the invention arethose which contain a combination of the meanings mentioned above asbeing preferred (preferable).

Especially preferred compounds of the formula (I) according to theinvention are those which contain a combination of the meaningsmentioned above as being especially preferred.

Very especially preferred compounds of the formula (I) according to theinvention are those which contain a combination of the meaningsmentioned above as being very especially preferred.

Hydrocarbon radicals such as alkyl or alkenyl--also in connection withhetero atoms such as alkoxy or alkylthio--in the definitions of radicalsmentioned hereinabove and hereinbelow are in each case straight-chain orbranched as far as this is possible.

If, for example, 5-amino-4-ethoxycarbonyl-3-ethyl-1-methylpyrazole and4-methoxyphenylacetyl chloride are used as starting materials whenpreparing compounds of the formula (I) in accordance with process (a),the course of the reaction can be represented by the following equation:##STR5##

If 5-(4-(4-chlorophenoxy)phenylacetylamino)-3-ethyl-1-methylpyrazole andsulphuryl chloride are used as starting materials when preparingcompounds of the formula (I) in accordance with process (b/α), thecourse of the reaction can be represented by the following equation:##STR6##

If 5-(4-(4-chlorophenoxy)phenylacetylamino)-3-ethyl-1-methylpyrazole andnitric acid, if appropriate in the presence of acetic acid, are used asstarting materials when preparing compounds of the formula (I) inaccordance with process (b/β), the course of the reaction can berepresented by the following equation: ##STR7##

The above-described process (a) for the preparation of compounds of theformula (I) is carried out in the presence of a diluent.

Diluents which can be employed are all customary solvents.

The following can preferably be used: optionally halogenated aliphaticor aromatic hydrocarbons, ethers or nitrites such as, for example,cyclohexane, toluene, chlorobenzene, chloroform, dichloromethane,dichloroethane, dioxane, tetrahydrofuran, diethyl ether or acetonitrile.

The above-described process (a) for the preparation of the compounds ofthe formula (I) is carried out in the presence of a base.

Bases which can be employed in process (a) are all customary protonacceptors. The following can preferably be used: alkali metal oralkaline earth metal hydroxides, alkali metal or alkaline earth metalcarbonates, alkali metal or alkaline earth metal hydrogen carbonates ornitrogen bases. Examples which may be mentioned are sodium hydroxide,calcium hydroxide, potassium carbonate, sodium hydrogen caronate,triethylamine, dibenzylamine, diisopropylamine, pyridine, quinoline,diazabicyclooctane (DABCO), diazabicyclonones (DBN) anddiazabicycloundecene (DBU).

The reaction temperatures in the above-described process (a) can bevaried within a substantial range. In general, the process is carriedout at temperatures between -40° C. and +200° C., preferably between 0°C. and 100° C.

When carrying out the above-described process (a) for the preparation ofthe compound of the formula (I), 1 to 2 mol, preferably 1 to 1.5 mol, ofacid halide of the formula (III) are generally employed per mol of5-aminopyrazole of the formula (II).

The end products are worked up and isolated in the generally knownmanner.

The above-described process (b/α) for the preparation of the compoundsof the formula (I) is carried out by means of a halogenating agent.

All customary halogenating agents may be employed for this purpose. Thefollowing can preferably be used: Cl₂, Br₂, hypohalous acids or saltsthereof such as, for example, sodium hypochlorite, potassiumhypochlorite, sodium hypobromite and potassium hypobromite, SO₂ Cl₂, S₂Cl₂, PCl₅ or N-bromosuccinimide.

If appropriate, the above-described process (b/α) for the preparation ofthe compounds of the formula (I) is carried out in the presence of adiluent. The following can preferably be used: optionally halogenatedaliphatic or aromatic hydrocarbons, ethers, nitriles or amides such as,for example, cyclohexane, toluene, chlorobenzene, chloroform,dichloromethane, dichloroethane, dioxane, tetrahydrofuran, diethylether, acetonitrile or dimethylformamide.

If appropriate, the above-described process (b/α) for the preparation ofthe compounds of the formula (I) is carried out in the presence of acatalyst. Suitable catalysts which can be employed are all acidic orbasic catalysts conventionally used for a halogenation reaction such as,for example, hydrogen halides or sodium acetate, and furthermorefree-radical initiators such as azoisobutyronitrile or dibenzoylperoxide.

When carrying out the above-described process (b/α), the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between -40° C. and 120° C.,preferably between 0° C. and 80° C.

When carrying out the above-described process (b/α) for the preparationof the compounds of the formula (I), 1 to 2 mol, preferably 1 to 1.5mol, of halogenating agent are generally employed per mol of acylated5-aminopyrazole of the formula (Ia).

The end products are worked up and isolated in the generally knownmanner.

The above-described process (b/β) for the preparation of the compoundsof the formula (I) is carried out using a nitrating reagent. Allcustomary nitrating reagents can be employed for this purpose. Thefollowing can preferably be used: nitric acid, if appropriate insulphuric acid, water, acetic acid or acetic anhydride, N₂ O₅ intetrachloromethane, methyl nitrate together with BF₃, sodium nitrite intrifluoroacetic acid or N₂ O₄.

If appropriate, the above-described process (b/β) for the preparation ofthe compounds of the formula (I) is carried out in the presence of adiluent. The following can preferably be used: optionally halogenatedhydrocarbons such as dichloromethane, chloroform, carbon tetrachlorideor chlorobenzene or nitrobenzene.

When carrying out the above-described process (b/β), the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between 0° C. and 100° C.,preferably between 0° C. and 40° C.

When carrying out the above-described process (b/β) for the preparationof the compounds of the formula (I), 1 to 5 mol, preferably 1 to 2 mol,of nitrating reagent are generally employed per mol of acylated5-aminopyrazole of the formula (Ia).

The end products are worked up and isolated in the generally knownmanner.

The starting materials of the formula (II) used in preparation process(a) are largely known (cf., for example, J. Org. Chem. 1956, 21, p. 1240et seq. and 1964, 29, p. 1915 et seq., and J. Chem. Research 1993, p. 76et seq.) or can be prepared by known methods (cf., for example, theabove references).

Hitherto unknown and also a subject of the present invention are5-aminopyrazoles of the formula (IIa) ##STR8## in which R¹, R³ and R⁴have the abovementioned meaning.

The new 5-aminopyrazoles of the formula (IIa) are obtained by reacting5-aminopyrazoles of the formula (IV) ##STR9## in which R¹, R³ and R⁴have the abovementioned meaning

with a chlorinating agent, preferably with sulphuryl chloride, in thepresence of aqueous hydrochloric acid in accordance with process (b/α).

The acid halides of the formula (III) furthermore to be used as startingmaterials in preparation process (a) are generally known compounds oforganic chemistry. In formula (III) Hal preferably represents chlorineor bromine.

The starting materials of the formula (Ia) used in preparation process(b) are compounds according to the invention and can be obtained inaccordance with the information given in preparation process (a).

Certain acylated 5-aminopyrazoles of the formula (I) can also beobtained when 5-aminopyrazole derivatives of the formula (Ib) ##STR10##in which R¹, R², R³ and R⁴ have the abovementioned meaning and

R⁷ represents the group --Y--R⁸ in which

Y has the abovementioned meaning and

R⁸ represents halogenoaryl, preferably iodo- or bromophenyl, especiallypreferably 4-iodo- or bromophenyl

are reacted with boronic acids of the formula (V)

    Ar--B(OH).sub.2                                            (V)

in which

Ar represents optionally substituted phenyl, suitable substituentspreferably, especially preferably or very especially preferably beingthose which have already been mentioned in the description of thecompounds of the formula (I) as being preferable, especially preferredor very especially preferred substituents for R⁶,

in the presence of a base such as, for example, potassium carbonate andin the presence of a diluent such as, for example, toluene, preferablyat the boiling point of the solvent used.

If, for example,5-(4-bromophenylacetyl)amino-4cyano-3-ethyl-1-methylpyrazole and4-trifluoromethoxyboronic acid are used as starting materials inaccordance with this process, the course of the reaction can berepresented by the following equation. ##STR11##

The substances of the formula (lb) are accessible for example by theprocess according to the invention for the preparation of substances ofthe formula (I) (cf. the preparation examples).

The compounds of the formula (V) are known and/or can be prepared in asimple manner by known processes.

The active compounds are suitable for controlling animal pests,preferably arthropods, in particular insects and arachnids, which arefound in agriculture, in forests, in the protection of stored productsand of materials, and in the hygiene sector. They are active againstnormally sensitive and resistant species and against all or some stagesof development. The abovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Pediculus humanus corporis,Haematopinus spp. and Linognathus spp.

From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.,Phemigus. spp., Phorodon humuli, Phylloxera vastatrix, Rhopalosiphumpadi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps,Lecanium corni, Saissetia oleae, Laodelphax striatellus, Niraparvatalugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. andPsylla spp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestrabrassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Acanthoscelides obtectus, Bruchidius obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis,Ceratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus andLatrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp.,Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.

The active compounds according to the invention are distinguished bypotent insecticidal and acaracidal activity.

In particular, compounds of the formula (I) according to the inventionare distinguished by an outstanding insecticidal activity. When employedagainst foliar and soil-dwelling insects, they show a potent activity,for example against mustard beetle lavae (Phaedon cochleariae), againstcaterpillars of the diamond-back moth (Plutella maculipennis) andcaterpillars of the fall armyworm (Spodoptera frugiperda), and againstthe green rice leafhopper (Nephotettix cincticeps).

The active compounds can be converted into the customary formulations,such as solutions, emulsions, suspensions, powders, dusts, pastes,soluble powders, granules, suspoemulsion concentrates, natural andsynthetic substances impregnated with active compounds andmicroencapsulations in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents and/orsolid carriers, optionally with the use of surfactants, that is,emulsifiers and/or dispersants, and/or foam formers.

In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. The following aremainly suitable as liquid solvents: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics or chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample mineral oil fractions, mineral and vegetable oils, alcohols suchas butanol or glycol and their ethers and esters, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents such as dimethylformamide and dimethylsulphoxide, or else water.

Suitable solid carriers are:

for example ground natural minerals such as kaolins, clays, talc, chalk,quartz, attapulgite, montmorillonite or diatomaceous earth, and groundsynthetic minerals such as highly-disperse silica, alumina andsilicates. Suitable solid carriers for granules are: for example crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, or else synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, maize cobs and tobacco stalks. Suitable emulsifiers and/or foamformers are: for example non-ionic and anionic emulsifiers such aspolyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers,for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates, or else protein hydrolysates. Suitabledispersants are: for example lignin-sulphite waste liquors andmethylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colourants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs suchas alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The active compound according to the invention may be present in itscommercially available formulations and in the use forms prepared fromthese formulations as a mixture with other active compounds such asinsecticides, attractants, sterilants, bactericides, acaricides,nematizides, fungicides, growth regulators or herbicides. Theinsecticides include, for example, phosphoric esters, carbamates,carboxylic esters, chlorinated hydrocarbons, phenyl ureas, substancesproduced by microorganisms, and others.

Examples of particularly advantageous components in mixtures are thefollowing:

Fungicides

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thizole-5-carboxanilide;2,6-dichloro-N-(4-trifluoromethylbenzyl)benzamide;(E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide;8-hydroxyquinoline sulphate; methyl(E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate;methyl (E)-methoximino[alpha-(o-tolyloxy)-o-tolyl]acetate;2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,

benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol,blasticidin-S, bromuconazole, bupirimate, buthiobate,

calcium polysulphide, captafol, captan, carbendazim, carboxin,quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate,cufraneb, cymoxanil, cyproconazole, cyprofuram,

dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran,diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole,dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine,drazoxolon, edifenphos, epoxyconazole, ethirimol, etridiazole,

fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam,ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole,flusilazole, flusulfamide, flutolanil, flutriafol, folpet,fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furmecyclox,guazatine,

hexachlorobenzene, hexaconazole, hymexazol,

imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione,isoprothiolane,

kasugamycin, copper preparations such as: copper hydroxide, coppernaphthenate, copper oxychloride, copper sulphate, copper oxide,oxine-copper and Bordeaux mixture,

mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl,metconazole, methasulfocarb, methfuroxam, metiram, metsulfovax,myclobutanil,

nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,

ofurace, oxadixyl, oxamocarb, oxycarboxin,

pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin,polyoxin, probenazole, prochloraz, procymidone, propamocarb,propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil,pyroquilon,

quintozene (PCNB),

sulphur and sulphur preparations,

tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole,thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid,triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole,tridemorph, triflumizole, triforine, triticonazole,

validamycin A, vinclozolin,

zineb; ziram.

Bactericides

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides

abamectin, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin,amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M,azocyclotin,

Bacillus thuringiensis,4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile,bendiocarb, benfuracarb, bensultap, betacyluthrin, bifenthrin, BPMC,brofenprox, bromophos A, bufencarb, buprofezin, butocarboxin,butylpyridaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,chloethocarb, chlorethoxyfos, chloretoxyfos, chlorfenvinphos,chlorfluazuron, chlormephos,N-[(6-chloro-3-pyridinyl)-methyl]-N'-cyano-N-methyl-ethanimidamide,chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezine,cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin,cypermethrin, cyromazine,

deltamethrin, demeton-M, demeton-S, demeton-S-methyl, diafenthiuron,diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,diflubenzuron, dimethoate,

dimethylvinphos, dioxathion, disulfoton,

edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox,ethoprophos, etofenprox, etrimphos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb,fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate,fenthion, fenvalerate, fipronil, fluazinam, flucycloxuron,flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos,formothion, fosthiazate, fubfenprox, furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion,ivermnectin,

lambda-cyhalothrin, lufenuron,

malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde, methacrifos,methamidophos, methidathion, methiocarb, methomyl, metolcarb,milbemectin, monocrotophos, moxidectin,

naled, NC 184, nitenpyram,

omethoate, oxamyl, oxydemethon M, oxydeprofos,

parathion A, parathion M, permethrin, phenthoate, phorate, phosalone,phosmet, phosphamdon, phoxim, pirimicarb, pirimiphos M, pirimiphos A,profenofos, profenophos, promecarb, propaphos, propoxur, prothiofos,prothoate, pymetrozin, pyrachlophos, pyraclofos, pyrachlophos,pyradaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen,pyriproxifen,

quinalphos,

salithion, sebufos, silafluofen, sulfotep, sulprofos,

tebufenozid, tebufenpyrad, tebupirimphos, teflubenzuron, tefluthrin,temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb,thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin,triarathen, triazophos, triazuron, trichlorfon, triflumuron,trimethacarb,

vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators are also possible.

Moreover, the active compound according to the invention can be presentin its commercially available formulations and in the use forms preparedfrom these formulations as a mixture with synergists. Synergists arecompounds by which the activity of the active compounds is increasedwithout it being necessary for the synergist added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide ranges. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.00001 and 1% byweight.

The use forms are employed in the customary manner which is adapted tosuit them.

When used against hygiene and stored-product pests, the active compoundis distinguished by an outstanding residual action on wood and clay andby a good stability to alkali on limed substrates.

Furthermore, it has been found that the compounds of the formula Iaccording to the invention have a potent insecticidal activity againstinsects which destroy industrial materials.

The following insects may be mentioned by way of example and as beingpreferred, but without limitation:

beetles, such as

Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobiumrufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobiusmollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctusplanicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale,Minthes rugicollis, Xyleborus spec. Tryptodendron spec. Apate monachus,Bostyrchus capucins, Heterobostrychus brunneus, Sinoxylon spec.Dinoderus minutus.

Dermapterans, such as

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.

Termites, such as

Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis,Coptotermes formosanus.

Bristletails,

such as Lepisma saccharina.

Industrial materials are to be understood as meaning, in the presentcontext, non-live materials such as, preferably, polymers, glues, sizes,papers and boards, leather, wood and derived timber products, andpaints.

The material to be protected against attack by insects is veryparticularly preferably wood and derived timber products.

Wood and derived timber products which can be protected by the agentaccording to the invention or by compositions comprising it are to beunderstood as meaning, for example, construction timber, wooden beams,railway sleepers, bridge components, jetties, wooden vehicles, boxes,pallets, containers, telephone poles, wood laggings, windows and doorsmade of wood, plywood, particle boards, joiner's work, or wood productswhich are generally used in construction or in joinery.

The active compounds can be used as such, in the form of concentrates orgenerally customary formulations, such as powders, granules, solutions,suspensions, emulsions or pastes.

The abovementioned formulations can be prepared in a manner known perse, for example by mixing the active compounds with at least one solventor diluent, emulsifier, dispersant and/or binder or fixative, waterrepellent, if appropriate desiccants and UV stabilizers and, ifappropriate, colourants and pigments and other processing auxiliaries.

The insecticidal compositions or concentrates used for the protection ofwood and timber products comprise the active compound according to theinvention in a concentration of 0.0001 to 95% by weight, in particular0.001 to 60% by weight.

The amount of the agents or concentrates employed depends on the speciesand the abundance of the insects, and on the medium. The optimum amountused can be determined in each case by test series. However, in generalit suffices to employ 0.0001 to 20% by weight, preferably 0.001 to 10%by weight, of the active compound based on the material to be protected.

The solvent and/or diluent used is an organochemical solvent or solventmixture and/or an oily or oil-like solvent or solvent mixture of lowvolatility and/or a polar organochemical solvent or solvent mixtureand/or water and, if appropriate, an emulsifier and/or wetting agent.

The organochemical solvents employed are preferably oily or oil-likesolvents with an evaporation number of above 35 and a flash point ofabove 30° C., preferably above 45° C. Substances which are used as suchoily and oil-like solvent of low volatility which are insoluble in waterare suitable mineral oils or their aromatic fractions andmineral-oil-comprising solvent mixtures, preferably white spirit,petroleum and/or alkylbenzene.

It is advantageous to use mineral oils with a boiling range of 170 to220° C., white spirit with a boiling range of 170 to 220° C., spindleoil with a boiling range of 250 to 350° C., petroleum or aromatics of aboiling range of 160 to 280° C., spirit of turpentine and the like.

In a preferred embodiment, the substances used are liquid aliphatichydrocarbons with a boiling range of 180 to 210° C. or high-boilingmixtures of aromatic and aliphatic hydrocarbons with a boiling range of180 to 220° C. and/or spindle oil and/or monochloronaphthaline,preferably α-monochloronaphthaline.

The organic oily or oil-like solvents of low volatility with anevaporation number of above 35 and a flash point of above 30° C.,preferably above 45° C., can be replaced in part by organochemicalsolvents of low or medium volatility, with the proviso that the solventmixture also has an evaporation number of above 35 and a flash point ofabove 30° C., preferably above 45° C., and that theinsecticide/fungicide mixture is soluble or emulsifiable in this solventmixture.

In a preferred embodiment, part of the organochemical solvent or solventmixture or an aliphatic polar organochemical solvent or solvent mixtureis replaced. Substances which are preferably used are aliphaticorganochemical solvents containing hydroxyl and/or ester and/or ethergroups, such as for example, glycol ethers, esters and the like.

Organochemical binders which are used within the scope of the presentinvention are the binding drying oils and/or synthetic resins which areknown per se, can be diluted with water and/or are soluble, dispersibleor emulsifiable in the organochemical solvents employed, in particularbinders composed of, or comprising, an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenol resin, hydrocarbon resin, such as indene-cumaroune resin,silicone resin, drying vegetable and/or drying oils and/or physicallydrying binders based on a natural and/or synthetic resin.

The synthetic resin used as binder can be employed in the form of anemulsion, dispersion or solution. Substances which can also be used asbinders are bitumen or bituminous substances in amounts of up to 10% byweight. In addition, colourants, pigments, water repellants, odoriferoussubstances and inhibitors or anticorrosives which are known per se canbe employed, inter alia.

The composition or concentrate preferably comprises, in accordance withthe invention, at least one alkyd resin or modified alkyd resin and/or adrying vegetable oil as the organochemical binder. Substances which arepreferably used according to the invention are alkyd resins with an oilcontent of over 45% by weight, preferably 50 to 68% by weight.

All or some of the abovementioned binder can be replaced by a fixative(mixture) or plasticizer (mixture). These additives are intended toprevent volatilization of the active compounds and crystallization orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of binder employed).

They plasticizers are from the chemical classes of the phthalic esters,such as dibutyl phthalate, dioctyl phthalate or benzylbutyl phthalate,the phosphoric esters, such as tributyl phosphate, the adipic esters,such as di(2-ethylhexyl) adipate, the stearates, such as butyl stearateor amyl stearate, the oleates, such as butyl oleate, the glycerol ethersor higher-molecular-weight glycol ethers, glycerol esters and p-toluenesulphonic esters.

Fixatives are based chemically on polyvinyl alkyl ethers such as, forexample, polyvinyl methyl ether, or ketones such as benzophenone orethylene benzophenone.

Another suitable solvent or diluent is, in particular, water, ifappropriate in a mixture with one or more of the abovementionedorganochemical solvents or diluents, emulsifiers and dispersants.

A particularly effective protection of wood is achieved by means ofindustrial-scale impregnating processes, for example vacuum,double-vacuum or pressure processes.

If appropriate, the ready-to-use compositions can comprise otherinsecticides and, if appropriate, also one or more fungicides.

Additional components which may be mixed are preferably the insecticidesand fungicides mentioned in WO 94/29 268. The compounds mentioned in theabove document are expressly part of the present application.

Components which may very particularly preferably be mixed areinsecticides, such as chloropyriphos, phoxim, silafluofin, alphamethrin,cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron and triflumuron,

and fungicides such as epoxyconazole, hexaconazole, azaconazole,propiconazole, tebuconazole, cyproconazole, metconazole, imazalil,dichlorfluanid, tolylfluanid, 3-iodo-2-propinyl butylcarbamate,N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one.

Preparation and use of the active compounds according to the inventioncan be seen from the examples which follow.

PREPARATION EXAMPLES Example 1 ##STR12## (Process a)

0.47 g (0.006 mol) of pyridine is added at room temperature to asolution 0.99 g (0.005 mol) of5-amino-4-ethoxycarbonyl-3-ethyl-1-methylpyrazole in 80 ml ofdichloromethane. A solution of 1.11 g (0.006 mol) of4-methoxyphenylacetyl chloride in 20 ml of dichloromethane issubsequently added dropwise at the same temperature. The mixture isstirred overnight at room temperature and subsequently, with reflux, for24 hours. When cold, the reaction mixture is washed with dilute HCl andwith dilute aqueous NaHCO₃ solution. The organic phase is dried overMgSO₄, filtered and evaporated to dryness.

This gives 1.28 g (74% of theory) of4-ethoxycarbonyl-3-ethyl-5-(4-methoxyphenylacetyl)amino-1-methylpyrazoleas a yellow solid of melting point 112 to 113° C.

Example 2 ##STR13## (Process a)

0.95 g (0.012 mol) of pyridine is added at room temperature to asolution of 1.25 g (0.01 mol) of 5-amino-3-ethyl-1-methylpyrazole in 120ml of dichloromethane. A solution of 3.37 g (0.012 mol) of4-(4-chlorophenoxy)phenylacetyl chloride in 30 ml of dichloromethane issubsequently added dropwise at the same temperature. After the mixturehas been stirred overnight at room temperature, it is washed insuccession with dilute HCl and dilute aqueous NaHCO₃ solution, and theproduct is dried over MgSO₄, filtered and evaporated to dryness.

This gives 3.10 g (84% of theory) of5-(4-(4-chlorophenoxy)phenylacetylamino)-3-ethyl-1-methylpyrazole as abrown oil.

¹ H NMR (CDCl₃): δ=1.19, 2.57, 3.56, 3.63, 3.73, 6.04, 6.92-7.03,7.27-7.33 ppm

Example 3 ##STR14## (Process b/α)

0.37 g (0.00275 mol) of sulphuryl chloride are added dropwise at 0° C.to a solution of 0.92 g (0.0025 mol) of5-(4-(4-chlorophenoxy)phenylacetylamino)-3-ethyl-1-methylpyrazole (Ex.2) in 10 ml of dichloromethane. After the mixture has been stirredovernight at room temperature, it is diluted with 10 ml ofdichloromethane and washed in succession with water, saturated aqueousNaHCO₃ solution and saturated aqueous NaCl solution, dried over MgSO₄,filtered and evaporated to dryness.

This gives 0.80 g (79% of theory) of4-chloro-5-(4-(4-chlorophenoxy)phenylacetylamino)-3-ethyl-1-methylpyrazoleas a brown oil.

¹ H NMR (CDCl₃): δ=1.21, 2.57, 3.63, 3.77, 6.82, 6.92-7.04, 7.30-7.35ppm

Example 4 ##STR15## (Process b/α)

0.44 g (0.00275 mol) of bromine are added dropwise at 0° C. to asolution of 0.92 g (0.0025 mol) of5-(4-(4-chlorophenoxy)phenylacetylamino)-3-ethyl-1-methylpyrazole (Ex.2) in 10 ml of dichloromethane. After the mixture has been stirredovernight at room temperature, it is diluted with 10 ml ofdichloromethane and washed in succession with water, saturated aqueousNaHCO₃ solution and saturated aqueous NaCl solution, dried over MgSO₄,filtered and evaporated to dryness.

This gives 0.90 g (80% of theory) of4-bromo-5-(4-(4-chlorophenoxy)phenylacetylamino)-3-ethyl-1-methylpyrazoleas a brown oil.

¹ H NMR (CDCl₃): δ=1.20, 2.56, 3.66, 3.77, 6.80, 6.91-7.04, 7.27-7.36ppm

Example 5 ##STR16## (Process a)

1.90 g (0.024 mol) of pyridine are added at room temperature to asolution of 3.19 g (0.02 mol) of5-amino-4-chloro-3-ethyl-1-methylpyrazole (Ex. IV-1) in 120 ml ofdichloromethane. A solution of 5.60 g (0.024 mol) of 4-bromophenylacetylchloride in 30 ml of dichloromethane is subsequently added dropwise atthe same temperature. The mixture is stirred overnight at roomtemperature and then washed with dilute HCl and dilute aqueous NaHCO₃solution. The organic phase is dried over MgSO₄, filtered and evaporatedto dryness.

This gives 4.61 g (63% of theory) of5-(4-bromophenylacetyl)amino4-chloro-3-ethyl-1-methylpyrazole as acolourless solid of melting point 167-168° C.

Preparation of the Starting Materials of Formula (IV) Example (IV-1)##STR17##

14.85 g (0.11 mol) of sulphuryl chloride are added dropwise at roomtemperature to a solution of 12.5 g (0.1 mol) of5-amino-3-ethyl-1-methylpyrazole in 100 ml of 20% strength HCl. Themixture is stirred for 40 hours at 60° C. After adding 7.43 g (0.055mol) of sulphuryl chloride, the mixture is stirred for a further 6 hoursat 60° C. After adding 2.97 g (0.022 mol) of sulphuryl chloride andstirring for a further 18 hours at 60° C., the mixture is treated withwater, the pH is brought to 9 using dilute aqueous NaOH solution, andthe mixture is extracted repeatedly with diethyl ether. The combinedorganic phases are dried over MgSO₄, filtered and evaporated to dryness.

This gives 13.47 g (84% of theory) of5-amino-4-chloro-3-ethyl-1-methylpyrazole as a pale yellow solid ofmelting point 50-51° C.

The following compounds of the formula (I) are obtained analogously orfollowing the general preparation instructions:

                                      TABLE 1                                     __________________________________________________________________________                                                           (1)                     ##STR18##                                                                    Ex.                                           Melting point or δ                                                      (ppm;                           No.                                                                              R.sup.1                                                                           R.sup.2                                                                              R.sup.3                                                                           R.sup.4                                                                          R.sup.5                  .sup.1 H NMR in                 __________________________________________________________________________                                                  CDCl.sub.3)                      6 CH.sub.3                                                                          CN     CH.sub.3                                                                          H                                                                                 ##STR19##               1.27; 2.22; 3.34; 3.57*)         7 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR20##               124-127° C.               8 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR21##               127-128° C.               9 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR22##               148-151° C.              10 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR23##               153-154° C.              11 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR24##               171-173° C.              12 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR25##               152-155° C.              13 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR26##               126-128° C.              14 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR27##               1.27; 1.68; 3.62; 3.77          15 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR28##               170-171° C.              16 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR29##               169-172° C.              17 C.sub.2 H.sub.5                                                                   H      CH.sub.3                                                                          H                                                                                 ##STR30##               1.19; 2.57; 3.73; 6.04          18 C.sub.2 H.sub.5                                                                   H      CH.sub.3                                                                          C.sub.2 H.sub.5                                                                   ##STR31##               1.13; 1.26; 2.64;  3.37;                                                      3.42; 5.91                      19 C.sub.2 H.sub.5                                                                   Cl     CH.sub.3                                                                          H                                                                                 ##STR32##               101-103° C.              20 C.sub.2 H.sub.5                                                                   Cl     CH.sub.3                                                                          C.sub.2 H.sub.5                                                                   ##STR33##               1.14; 1.28; 2.66                21 C.sub.2 H.sub.5                                                                   Br     CH.sub.3                                                                          H                                                                                 ##STR34##               111-112° C.              22 C.sub.2 H.sub.5                                                                   Br     CH.sub.3                                                                          C.sub.2 H.sub.5                                                                   ##STR35##               1.15; 1.28; 3.29                23 C.sub.2 H.sub.5                                                                   NO.sub.2                                                                             CH.sub.3                                                                          H                                                                                 ##STR36##               1.24; 2.89; 3.76;  3.83;                                                      8.48                            24 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                   CH.sub.3                                                                          H                                                                                 ##STR37##               1.20; 1.28; 1.32;  2.78;                                                      3.69; 3.75;  4.20               25 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                   CH.sub.3                                                                          H                                                                                 ##STR38##               133-135° C.              26 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                   CH.sub.3                                                                          H                                                                                 ##STR39##               1.21; 1.32; 2.76:  3.68;                                                      3.73; 4.25:  8.44               27 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                   CH.sub.3                                                                          H                                                                                 ##STR40##               156-158° C.              28 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                   CH.sub.3                                                                          H                                                                                 ##STR41##               1.22; 1.35; 2.74;  3.56;                                                      4.28; 5.04                      29 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                   CH.sub.3                                                                          H                                                                                 ##STR42##               1.21; 1.32; 2.78;  3.70;                                                      3.76; 4.25                      30 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                   CH.sub.3                                                                          H                                                                                 ##STR43##               1.21; 1.32; 2.78;  3.71;                                                      3.77; 4.25;  8.48               31 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                   CH.sub.3                                                                          H                                                                                 ##STR44##               145-147° C.              32 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                   CH.sub.3                                                                          H                                                                                 ##STR45##               114-117° C.              33 C.sub.2 H.sub.5                                                                   Cl     CH.sub.3                                                                          H                                                                                 ##STR46##               150-151° C.              34 C.sub.2 H.sub.5                                                                   Cl     CH.sub.3                                                                          H                                                                                 ##STR47##               147° C.                  35 C.sub.2 H.sub.5                                                                   Cl     CH.sub.3                                                                          H                                                                                 ##STR48##               147° C.                  36 C.sub.2 H.sub.5                                                                   H      CH.sub.3                                                                          H                                                                                 ##STR49##               1.20; 2.56; 3.58;  3.76;                                                      6.05                            37 C.sub.2 H.sub.5                                                                   --COOCH.sub.3                                                                        CH.sub.3                                                                          H                                                                                 ##STR50##               162° C.                  38 C.sub.2 H.sub.5                                                                   --COOCH.sub.3                                                                        CH.sub.3                                                                          H                                                                                 ##STR51##               1.21; 2.71; 3.73;  3.78;                                                      3.82                            39 C.sub.2 H.sub.5                                                                   --COOCH.sub.3                                                                        CH.sub.3                                                                          H                                                                                 ##STR52##               1.20; 2.79; 3.71;  3.76;                                                      3.78                            40 C.sub.2 H.sub.5                                                                   Br     CH.sub.3                                                                          H                                                                                 ##STR53##               134° C.                  41 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                          CH.sub.3                                                                          ##STR54##               1.29; 2.90; 3.15;  3.41;                                                      3.43; 4.22                      42 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                          CH.sub.3                                                                          ##STR55##               1.29; 2.74; 3.16;  3.44;                                                      3.45; 4.22                      43 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                          CH.sub.3                                                                          ##STR56##               1.28; 2.90; 3.13;  3.34;                                                      3.41; 4.20                      44 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                          H                                                                                 ##STR57##               1.32; 2.77; 3.70;  3.75;                                                      4.23;                           45 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR58##               1.31; 2.67; 3.61;  3.76;        46 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                          H                                                                                 ##STR59##               1.21; 1.33; 2.76;  3.71;                                                      3.80; 4.22                      47 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR60##               62-64° C.                48 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                          H                                                                                 ##STR61##               1.20; 1.30; 2.48;  2.76;                                                      3.70; 3.75;  4.23               49 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR62##               53-54° C.                50 CH.sub.3                                                                          CN     CH.sub.3                                                                          H                                                                                 ##STR63##               101° C.                  51 CH.sub.3                                                                          CN     CH.sub.3                                                                          H                                                                                 ##STR64##               102-104° C.              52 CH.sub.3                                                                          CN     CH.sub.3                                                                          H                                                                                 ##STR65##               135-138° C.              53 CH.sub.3                                                                          --COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                          H                                                                                 ##STR66##               141-142° C.              54 CH.sub.3                                                                          --COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                          H                                                                                 ##STR67##               142-144° C.              55 CH.sub.3                                                                          --COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                          H                                                                                 ##STR68##               1.32; 2.36; 3.70;  3.76;                                                      4.25                            56 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                          H                                                                                 ##STR69##               1.22; 1.36; 2.80;  3.70;                                                      4.29                            57 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR70##               62-64° C.                58 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                          H                                                                                 ##STR71##               1.21; 1.29; 2.76;  3.69;                                                      3.75                            59 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR72##               58-60° C.                60 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                          H                                                                                 ##STR73##               81° C.                   61 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR74##               133° C.                  62 C.sub.2 H.sub.5                                                                   --COOC.sub.3 H.sub.7 -i                                                              CH.sub.3                                                                          H                                                                                 ##STR75##               126-128° C.              63 C.sub.2 H.sub.5                                                                   --COOC.sub.3 H.sub.7 -i                                                              CH.sub.3                                                                          H                                                                                 ##STR76##               82° C.                   64 C.sub.2 H.sub.5                                                                   --COOC.sub.3 H.sub.7 -i                                                              CH.sub.3                                                                          H                                                                                 ##STR77##               75° C.                   65 C.sub.2 H.sub.5                                                                   CN     C.sub.4 H.sub.9 -t                                                                H                                                                                 ##STR78##               165-167° C.              66 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                          H                                                                                 ##STR79##               126-128° C.              67 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR80##               105-107° C.              68 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 C.sub.4 H.sub.9 -t                                                                H                                                                                 ##STR81##               184° C.                  69 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 C.sub.4 H.sub.9 -t                                                                H                                                                                 ##STR82##               171° C.                  70 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                          H                                                                                 ##STR83##               120° C.                  71 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR84##               178° C.                  72 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                          H                                                                                 ##STR85##               131° C.                  73 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR86##               163° C.                  74 C.sub.2 H.sub.5                                                                   --COOCH.sub.2 -  CH═CH.sub.2                                                     CH.sub.3                                                                          H                                                                                 ##STR87##               121° C.                  75 C.sub.2 H.sub.5                                                                   --COOCH.sub.2 -  CH═CH.sub.2                                                     CH.sub.3                                                                          H                                                                                 ##STR88##               1.22; 2.79;  3.73; 3.81;        76 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 C.sub.3 H.sub.7 -i                                                                H                                                                                 ##STR89##               125-127° C.              77 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 C.sub.3 H.sub.7 -i                                                                H                                                                                 ##STR90##               124° C.                  78 C.sub.2 H.sub.5                                                                   CN     C.sub.3 H.sub.7 -i                                                                H                                                                                 ##STR91##               168° C.                  79 C.sub.2 H.sub.5                                                                   CN     C.sub.3 H.sub.7 -i                                                                H                                                                                 ##STR92##               190-192° C.              80 C.sub.4 H.sub.9 -t                                                                H      CH.sub.3                                                                          H                                                                                 ##STR93##               70-71° C.                81 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                          H                                                                                 ##STR94##               186-187° C.              82 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR95##               168° C.                  83 C.sub.4 H.sub.9 -t                                                                Br     CH.sub.3                                                                          H                                                                                 ##STR96##               95° C.                   84 C.sub.4 H.sub.9 -t                                                                Cl     CH.sub.3                                                                          H                                                                                 ##STR97##               1.34; 3.65;  3.81               85 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                          H                                                                                 ##STR98##               85° C.                   86 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR99##               110-111° C.              87 C.sub.2 H.sub.5                                                                   --COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                          H                                                                                 ##STR100##              1.21; 1.33;  2.79; 3.72;                                                      3.79                            88 C.sub.2 H.sub.5                                                                   CN     CH.sub.3                                                                          H                                                                                 ##STR101##              1.25; 2.67;  3.63;              __________________________________________________________________________                                                  3.79                        

Use Examples Example A

Phaedon Larvae Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of the active compound of the desired concentration andpopulated with mustard beetle larvae (Phaedon cochleariae), while theleaves are still moist.

After the desired period of time, the destruction in % is determined.100% means that all the beetle larvae have been killed; 0% means thatnone of the beetle larvae have been killed.

In this test, a destruction of 100% is caused, after 7 days, for exampleby the compounds of Preparation Examples 2, 3, 9, 10, 11, 12, 13, 15,16, 29, 31 and 32 at an exemplary active compound concentration of 0.1%.

Example B

Plutella Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compond, 1 part by weight ofactive compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration andpopulated with caterpillars of the diamond-back moth Plutellamaculipennis while the leaves are still moist.

After the desired period of time, the destruction in % is determined.100% means that all the caterpillars have been killed; 0% means thatnone of the caterpillars have been killed.

In this test, a destruction of 100% is caused, after 7 days, for exampleby the compounds of Preparation Examples 2, 3, 12, 13, 15, 16, 29, 31and 32 at an exemplary active compound concentration of 0.1%.

Example C

Spodoptera Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration andpopulated with caterpillars of the fall armyworm (Spodopterafrugiperda), while the leaves are still moist.

After the desired period of time, the destruction in % is determined.100% means that all the caterpillars have been killed; 0% means thatnone of the caterpillars have been killed.

In this test, a destruction of 100% is caused, after 7 days, for exampleby the compounds of Preparation Examples 2, 6, 13, 15, 16, 31 and 32 atan exemplary active compound concentration of 0.1%.

Example D

Nephotettix Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compond, 1 part by weight ofactive compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Rice seedlings (Oryza sativa) are treated by being dipped into thepreparation of active compound of the desired concentration andpopulated with caterpillars of the green rice leafhopper (Nephotettixcincticeps) while the leaves are still moist.

After the desired period of time, the destruction in % is determined.100% means that all the leafhoppers have been killed; 0% means that noneof the leafhoppers have been killed.

In this test, a destruction of at least 90% was caused, after 6 days,for example by the compounds of Preparation Examples 13, 29, 31 and 32at an exemplary active compound concentration of 0.1%.

What is claimed is:
 1. Compounds of the formula (I) ##STR102## in whichR¹ represents alkyl, alkoxyalkyl or halogenoalkyl,R² represents halogen,cyano, nitro, halogenoalkylthio, alkoxycarbonyl or alkenyloxycarbonyl,R³ represents alkyl or optionally substituted cycloalkyl, R⁴ representshydrogen, alkyl or optionally substituted cycloalkyl and R⁵ representsthe group --Y--R⁶, whereinY represents C₁ -C₄ -alkanediyl, which isoptionally substituted by halogen or C₃ -C₆ -cycloalkyl and R⁶represents phenyl, which is optionally mono-substituted totri-substituted by identical or different substituents selected from thegroup consisting of halogen, nitro, cyano, C₁ -C₁₂ -alkyl, C₁ -C₁₂-alkoxy and C₁ -C₁₂ -alkylthio.
 2. Compounds of the formula (I)according to claim 1 in whichR¹ represents C₁ -C₄ -alkyl, C₁ -C₄-alkoxy-C₁ -C₄ -alkyl or C₁ -C₄ -halogenoalkyl, R² represents halogen,cyano, nitro, trifluoromethylthio, difluoromethylthio, C₁ -C₄-alkoxy-carbonyl or C₂ -C₄ -alkenyloxycarbonyl, R³ represents C₁ -C₄-alkyl, or represents C₃ -C₆ -cycloalkyl which is optionally substitutedby halogen or C₁ -C₄ -alkyl, R⁴ represents hydrogen, C₁ -C₄ -alkyl, orrepresents C₃ -C₆ -cycloalkyl which is optionally substituted by halogenor C₁ -C₄ -alkyl, R⁵ represents the group --Y--R⁶ whereinY represents C₁-C₄ -alkanediyl, which is optionally substituted by halogen or C₃ -C₆-cycloalkyl and R⁶ represents phenyl, which is optionallymono-substituted to tri-substituted by identical or differentsubstituents selected from the group consisting of halogen, nitro,cyano, C₁ -C₁₂ -alkyl, C₁ -C₁₂ -alkoxy and C₁ -C₁₂ -alkylthio. 3.Compounds of the formula (I) according to claim 1, in whichR¹ representsmethyl, ethyl, n- or i-propyl or n-, i-, s- or t-butyl; or representsmethoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, trifluoromethyl,difloromethyl, fluoromethyl, 1-chloro-1-ethyl or 1-fluoro-1-ethyl, R²represents fluorine, chlorine, bromine, cyano, nitro,trifluoromethylthio, difluoromethylthio, methoxycarbonyl,ethoxycarbonyl, n- or i-propoxycarbonyl, n-, i-, s- or t-butoxycarbonylor allyloxycarbonyl, R³ represents methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, or represents -cyclopropyl, cyclopentyl orcyclohexyl, each of which is optionally substituted by fluorine,chlorine, methyl and/or ethyl, R⁴ represents hydrogen, methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, or represents cyclopropyl,cyclopentyl or cyclohexyl, each of which is optionally substituted byfluorine, chlorine, methyl and/or ethyl, R⁵ represents the group--Y--R⁶, whereinY represents C₁ -C₄ -alkanediyl, which is optionallysubstituted by halogen or C₃ -C₆ -cycloalkyl and R⁶ represents phenyl,which is optionally mono-substituted to tri-substituted by identical ordifferent substituents selected from the group consisting of halogen,nitro, cyano, C₁ -C₁₂ -alkyl, C₁ -C₁₂ -alkoxy and C₁ -C₁₂ -alkylthio. 4.Compounds of the formula (I) according to claim 1 in whichR¹ representsmethyl, ethyl, i-propyl, t-butyl, methoxymethyl, 1-chloro-1-ethyl or1-fluoro-1-ethyl, R² represents chlorine, bromine, cyano, nitro,methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl or allyloxycarbonyl,R³ represents methyl, ethyl, i-propyl, t-butyl, or cyclopropyl, R⁴represents hydrogen, methyl, ethyl, i-propyl or cyclopropyl, R⁵represents the group --Y--R⁶, whereinY represents C₁ -C₄ -alkanediyl,which is optionally substituted by halogen or C₃ -C₆ -cycloalkyl and R⁶represents phenyl, which is optionally mono-substituted totri-substituted by identical or different substituents selected from thegroup consisting of halogen nitro, cyano, C₁ -C₁₂ -alkyl, C₁ -C₁₂-alkoxy and C₁ -C₁₂ -alkylthio.
 5. Process for the preparation ofcompounds of the formula (I) according to claim 1, whereina)5-aminopyrazoles of the formula (II) ##STR103## in which R¹, R², R³ andR⁴ have the meaning given in claim 1are reacted with acid halides of theformula (III)

    R.sup.5 --CO--Hal                                          (III)

in which R⁵ has the meaning given in claim 1 and Hal representshalogenin the presence of a base and in the presence of a diluent; or b)acylated 5-aminopyrazoles of the formula (Ia) ##STR104## in which R¹,R³, R⁴ and R⁵ have the abovementioned meaningare reacted (α) with ahalogenating agent, if appropriate in the presence of a diluent and ifappropriate in the presence of a catalyst,or (β) with a nitrating agent,if appropriate in the presence of a diluent.
 6. A pestical compositioncomprising a pesticidally effective amount of a compound according toclaim 1 and a diluent.
 7. A method of combatting unwanted pests whichcomprises administering to such pests or to a locus from which it isdesired to exclude such pests a pesticidally effective amount of acompound according to claim
 1. 8. A compound of the formula (I)##STR105## in which

    ______________________________________                                        R.sup.1                                                                             R.sup.2                                                                              R.sup.3 R.sup.4                                                                            R.sup.5                                             ______________________________________                                        CH.sub.3                                                                            CN     CH.sub.3                                                                              H                                                                                   ##STR106##                                         ______________________________________                                    